CN111987290B - Preparation method and application of lithium/lithiated metal oxide framework composite structure negative electrode - Google Patents
Preparation method and application of lithium/lithiated metal oxide framework composite structure negative electrode Download PDFInfo
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- CN111987290B CN111987290B CN202010916546.7A CN202010916546A CN111987290B CN 111987290 B CN111987290 B CN 111987290B CN 202010916546 A CN202010916546 A CN 202010916546A CN 111987290 B CN111987290 B CN 111987290B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
- H01M4/382—Lithium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method and application of a lithium/lithiated metal oxide framework composite structure negative electrode, wherein the method comprises the following steps: firstly, MO is mixedxUniformly coating the mixture of conductive carbon and PVDF on a current collector, and drying in vacuum to obtain MOxPole pieces; secondly, taking a metal lithium sheet as a negative electrode, MOxThe pole piece is used as a counter electrode, a battery is assembled, constant current discharge is carried out, the cut-off voltage is controlled, and Li is obtainedyMOxAn electrode frame; thirdly, mixing LiyMOxThe electrode frame is mixed with molten lithium to obtain a composite structure negative electrode, and the solid electrolyte is adopted to assemble the all-solid-state battery. The invention relates to an embedded transition metal oxide MOxAs a carrier, Li having a fast ion transport property is formed after lithium intercalation thereofyMOxAnd the metal lithium is uniformly deposited in the electrode frame, so that the growth of lithium dendrites is inhibited, and safety accidents are avoided.
Description
Technical Field
The invention belongs to the technical field of energy storage, and relates to a preparation method and application of a rapid ion transmission type lithium/lithiated metal oxide framework composite structure cathode for a lithium secondary all-solid-state battery.
Background
Lithium metal is due to its lowest electrode potential (-3 relative to a standard hydrogen electrode.04V), higher specific mass capacity (3860 mAh/g) and highest specific area capacity (2060 mAh/cm)2) Has great development prospect. However, lithium dendrites are also generated in the solid-state battery due to uneven deposition of lithium ions, and the growing of the lithium dendrites may pierce the solid-state electrolyte to cause short-circuiting of the battery, and in a serious case, may cause safety problems such as fire and even explosion.
The main measures for inhibiting the growth of lithium dendrites include an artificial Solid Electrolyte Interface (SEI) film, a 3D current collector, and the like. However, artificial SEI films tend to act only on lithium deposition on the electrode surface, and do not significantly act when bulk lithium participates in the battery reaction. And the 3D current collector is often a single conductive framework, and the inhibition effect on lithium dendrites is insufficient.
Therefore, it is desired to develop a lithium metal negative electrode with low cost and good effect of suppressing lithium dendrites to improve the battery performance and safety of the lithium metal solid-state battery.
Disclosure of Invention
The invention aims to provide a rapid ion transmission type lithium/lithiated metal oxide framework composite structure cathode for a lithium secondary all-solid-state battery, which has low cost and good cycle performance and inhibits dendritic crystal growth, and the all-solid-state battery. Compared with the traditional lithium cathode, the cathode with the rapid ion transmission type lithium/lithiated metal oxide frame composite structure designed by the invention uses the frame with the rapid ion transmission characteristic obtained by in-situ lithiation, has better capability of inhibiting lithium dendrite, and the lithium is dissolved and deposited in the electrode frame, so that the safety performance and the cycle performance of the battery are improved.
The purpose of the invention is realized by the following technical scheme:
a method for preparing a negative electrode with a lithium/lithiated metal oxide framework composite structure, as shown in fig. 1, comprises the following steps:
step one, an embedded transition metal oxide powder MOxThe conductive carbon and PVDF are mixed and then uniformly coated on the current collectorDrying in vacuum at 60-100 ℃ on a body to obtain MOxPole piece, wherein: embedded transition metal oxide powder MOxIs TiO, TiO2、Ti2O3、NbO、NbO2、Nb2O3、Nb2O5、MoO、MoO2、MoO3、VO、VO2、V2O3、V2O5、MnO、MnO2、Mn2O3、Mn3O4One of (1), MOxThe mass ratio of the conductive carbon to the PVDF is 7-9: 0.5-2: 0.5-1, and the current collector is a Cu foil;
step two, taking a metal lithium sheet as a negative electrode, MOxThe pole piece is used as a counter electrode, a battery is assembled, constant current discharge is carried out, the cut-off voltage is controlled, and lithium ions are uniformly inserted into MOxIn the material, Li is obtainedyMOxAn electrode frame, wherein: the current density of constant current discharge is 0.1-1 mA g-1The cut-off voltage is 0.01-1.5V;
step three, in a glove box, adding LiyMOxMixing the electrode frame with molten lithium to infuse the molten Li into the LiyMOxAnd obtaining the cathode with a rapid ion transmission type lithium/lithiated metal oxide framework composite structure inside the electrode framework, wherein: liyMOxThe temperature of mixing the electrode frame and the molten lithium is 250-300 ℃.
The lithium/lithiation metal oxide framework composite structure negative electrode prepared by the method is used as a negative electrode, a lithium battery positive electrode material is used as a positive electrode, and a solid electrolyte is used as an electrolyte, so that the lithium secondary all-solid-state battery is obtained, wherein: the lithium battery positive electrode material is any one of lithium iron phosphate, ternary lithium manganate and lithium cobaltate, and the solid electrolyte is any one of polymer solid electrolyte and inorganic solid electrolyte.
In the present invention, LiyMOxThe electrode frame is provided with a large number of pores, lithium can be stored in advance, the amount of the stored lithium can be regulated and controlled through the amount of the molten lithium, and LiyMOxThe mass ratio of (A) to (B) is 0.5-2: 1.
in the present invention, LiyMOxElectrode frameThe frame has a higher lithium ion transmission speed, and can even the lithium ion flux in circulation, thereby achieving the purpose of inhibiting lithium dendrite. Meanwhile, the deposition and dissolution of lithium occur inside the electrode frame, and the safety performance of the battery is improved.
The invention relates to an embedded transition metal oxide MOx(M = Ti, Nb, Mo, V, Mn, etc.) as a carrier, which forms Li having a rapid ion transport property after lithium intercalationyMOxAnd the metal lithium is uniformly deposited in the electrode frame, so that the growth of lithium dendrites is inhibited, and safety accidents are avoided. Compared with the prior art, the invention has the following advantages:
1、LiyMOxthe electrode frame is relatively inexpensive.
2、LiyMOxThe electrode frame can provide a uniform lithium flux.
3、LiyMOxThe electrode frame has a good effect of inhibiting lithium dendrites.
4. The lithium loading capacity in the composite structure negative electrode is controllable.
5. The assembled full battery has better cycle performance and potential for industrial application.
Drawings
FIG. 1 is a schematic diagram of the preparation process of the negative electrode with a rapid ion transport type lithium/lithiated metal oxide framework composite structure of the present invention, MOxAfter lithium intercalation, the molten lithium metal is infused into LiyMOxInside the electrode frame.
FIG. 2 shows Li in exampleyMnO2And testing the cycle performance of the lithium/lithiated metal oxide framework composite structure negative electrode symmetrical battery.
Fig. 3 is an SEM image of the fast ion transport lithium/lithiated metal oxide framework composite structure negative electrode of example 1 after lithium deposition.
Detailed Description
The technical solutions of the present invention are further described below with reference to the following examples, but the present invention is not limited thereto, and any modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Example 1
The embodiment provides a preparation method of a rapid ion transmission type lithium/lithiated metal oxide framework composite structure negative electrode for a lithium secondary battery, which comprises the following specific steps:
(1) MnO of2Mixing the powder, the conductive carbon and the PVDF according to the ratio of 7:2:1, magnetically stirring for 12 hours to uniformly mix the powder, the conductive carbon and the PVDF, uniformly coating the uniformly mixed slurry on the surface of the copper foil by using a scraper, transferring the copper foil to a vacuum oven, and drying the pole piece in vacuum at 60 ℃ for 12 hours.
(2) Taking a lithium sheet as a negative electrode, taking the pole sheet prepared in the step (1) as a counter electrode, and taking 0.5 mA g-1The current density of (2) was subjected to constant current discharge at a cut-off voltage of 1.5V to obtain LiyMnO2Y is more than or equal to 0.5 and less than or equal to 0.75.
(3) The Li obtained in the step (2)yMnO2Electrode frame and molten lithium (Li)yMnO2: li =1: 2) recombination at 300 ℃, pouring molten lithium into LiyMnO2And obtaining the cathode with a rapid ion transmission type lithium/lithiation metal oxide framework composite structure inside the electrode framework.
Li prepared in this exampleyMnO2The cycle performance test of the lithium/lithiated metal oxide framework composite structure negative electrode symmetric battery is shown in figure 2, and the current density is 0.1mA cm-1Capacity of 0.1mAh cm-1。
The negative electrode with the rapid ion transport type lithium/lithiated metal oxide framework composite structure obtained in the embodiment is used as a negative electrode, lithium iron phosphate is used as a positive electrode, and Li3InCl6And assembling the solid electrolyte to form the all-solid-state battery. After the all-solid-state battery is cycled for 10 times, the battery is opened and SEM observation is carried out, as shown in figure 3, the situation that no dendrite is generated on the surface of the pole piece and the metal lithium is stored in Li can be seenyMnO2Within the electrode frame.
Example 2
The embodiment provides a preparation method of a rapid ion transmission type lithium/lithiated metal oxide framework composite structure negative electrode for a lithium secondary battery, which comprises the following specific steps:
(1) adding MoO2Mixing the powder, the conductive carbon and the PVDF according to the ratio of 7:2:1, magnetically stirring for 24 hours to uniformly mix the powder, the conductive carbon and the PVDF, uniformly coating the uniformly mixed slurry on the surface of the copper foil by using a scraper, transferring the copper foil to a vacuum oven, and drying the pole piece in vacuum at 80 ℃ for 12 hours.
(2) Taking a lithium sheet as a negative electrode, taking the pole sheet prepared in the step (1) as a counter electrode, and taking 0.5 mA g-1The current density of (2) was subjected to constant current discharge at a cut-off voltage of 1.5V to obtain LiyTiO2Y is more than or equal to 0.5 and less than or equal to 0.75.
(3) The Li obtained in the step (2)yTiO2Electrode frame and molten lithium (Li)yTiO2: li =1: 2) recombination at 300 ℃, pouring molten lithium into LiyTiO2And obtaining the novel rapid ion transmission type lithium/lithiation metal oxide framework composite structure cathode inside the electrode framework.
The negative electrode having a rapid ion transport type lithium/lithiated metal oxide framework composite structure obtained in this example was used as a negative electrode, and Li was added3InCl6And assembling the solid electrolyte to form the all-solid-state battery.
Claims (9)
1. A method of making a lithium/lithiated metal oxide framework composite structure negative electrode, the method comprising the steps of:
step one, an embedded transition metal oxide powder MOxUniformly coating the mixture of conductive carbon and PVDF on a current collector, and drying at 60-100 ℃ in vacuum to obtain MOxPole piece, the embedded transition metal oxide powder MOxIs TiO, TiO2、Ti2O3、NbO、NbO2、Nb2O3、Nb2O5、MoO、MoO2、MoO3、VO、VO2、V2O3、V2O5、MnO、MnO2、Mn2O3、Mn3O4One of (1);
step two, taking a metal lithium sheet as a negative electrode, MOxThe pole piece is used as a counter electrode, a battery is assembled, constant current discharge is carried out, the cut-off voltage is controlled, and lithium ions are uniformly inserted into MOxIn the material, Li is obtainedyMOxAn electrode frame;
step three, in a glove box, adding LiyMOxMixing the electrode frame with molten lithium to infuse the molten Li into the LiyMOxAnd obtaining the cathode with a rapid ion transmission type lithium/lithiation metal oxide framework composite structure inside the electrode framework.
2. The method of making a lithium/lithiated metal oxide framework composite structure negative electrode of claim 1, characterized in that said MO isxThe mass ratio of the conductive carbon to the PVDF is 7-9: 0.5-2: 0.5-1.
3. The method of making a lithium/lithiated metal oxide framework composite structure negative electrode of claim 1, wherein the current collector is a Cu foil.
4. The method for preparing the negative electrode with the lithium/lithiated metal oxide framework composite structure according to claim 1, wherein the current density of the constant current discharge is 0.1 to 1mA g-1The cut-off voltage is 0.01 to 1.5V.
5. The method of making a lithium/lithiated metal oxide framework composite structure negative electrode of claim 1, characterized in that the LiyMOxThe temperature of mixing the electrode frame and the molten lithium is 250-300 ℃.
6. The method of making a lithium/lithiated metal oxide framework composite structure negative electrode of claim 1, characterized in that Li and Li in step threeyMOxThe mass ratio of (A) to (B) is 0.5-2: 1.
7. use of a lithium/lithiated metal oxide framework composite structured negative electrode prepared by the method of any one of claims 1 to 6 in a lithium secondary all-solid-state battery.
8. The use of the lithium/lithiated metal oxide framework composite structure negative electrode according to claim 7 in a lithium secondary all-solid-state battery, wherein the lithium secondary all-solid-state battery uses the lithium/lithiated metal oxide framework composite structure negative electrode as a negative electrode, a lithium battery positive electrode material as a positive electrode, and a solid electrolyte as an electrolyte.
9. The application of the lithium/lithiated metal oxide framework composite structure negative electrode in a lithium secondary all-solid-state battery according to claim 8, wherein the lithium battery positive electrode material is any one of lithium iron phosphate, ternary lithium manganate and lithium cobaltate, and the solid electrolyte is any one of a polymer solid electrolyte and an inorganic solid electrolyte.
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